ANSWERS

1)
OH

+ enantiomer
OCH3

2)
CH3

Cl

3)
Cl (R/S)

4)

Cl

5)

(R/S)
Br

6)
Cl

7)
OH

CH3

8)
OH

(R/S)

9)

OH
10)
HO
CH3
11)
OH

(R/S)

12)
OCH3

13)
CH3

+ enantiomer

OH
14)

or simply (R/S)

HO H HO

15)

16)
Br
CH3

+ enantiomer
Br

17)
Cl H
CH2CH3
H
+ enantiomer
H3C Cl
18)
OH
Cl

19)
OH
CH3
+ enantiomer

OH

20)
O
H CH2CH3
+ enantiomer
H3C H
21)
OH

CH3 + enantiomer

OH

22)
O

CHO
H 3C

23)
O O

+
OH
24)
CHO O

+
H

25) B

26) This mechanism is best approached by working backwards. The product shown is an ether-bromide,
with the oxygen and the bromine atoms on adjacent carbons. Every time two functional groups are on
adjacent carbons it suggests the possibility that they might be formed by an addition to the C=C double
bond. This can be represented generically thus:

+ A B

A B

An addition of bromine in the presence of water produces such result, adding Br to one carbon and
OH to the other (section 8-11 in the textbook).

Br2
H 2O
OH Br

This suggests the possibility that an alcohol could be used instead of water, with similar results,
except that this would add Br to one carbon and RO to the other one.

Br2
ROH
OR Br

The mechanism of this reaction would be similar to that with water. Bromine adds first to form a
three memebered ring intermediate, followed by nucleophilic attack by the alcohol from the back.
Let’s use an unsymmetrical alkene to illustrate the point that the most highly substituted carbon gets
the RO group preferentially.
 R H
O
+ HO R Br RO
Br Br
+ HBr
Br Br
Br

The molecule in question has an oxygen (ether group) and a bromine on adjacent carbons. We can
make a similar reasoning as above that such arrangement forms from the reaction between a C=C
bond and Br2 in the presence of an alcohol, a group that also happens to be present in the starting
material.

1
Br
2
3 4 2
O HO 53
1
4
5

The ether and bromine groups are on adjacent

carbons, suggesting that the original double bond The starting material also happens to have
was between C1 and C2. Notice the oxygen on C5 5 carbons, with the double bond on C1 and C2,
and the oxygen on C5.

With this scenario in place, we can now start the mechanism from the first step, which would be the
attack of the pi-bond on bromine to form a three membered ring intermediate.

4
HO 5 3
4 Br
2 HO 5 3
1 + Br Br 2 + Br
1

The alcohol group is now poised to attack the three membered ring at the most highly substituted
carbon. The carbon chain is long enough to allow for flexibility of movement without introducing
strain.

3 3 Br
4 Br
2 4 3
2 1
2
5 4
O 1 1 + Br Br + HBr
O H O
H 5 5

27) When the starting material gets placed in acid, two (basic) sites can get protonated: the oxygen atom
and the pi-bond. The pi-bond is a weak base,. Energy must be expended to break it in order to protonate it
and form a carbocation. The oxygen is also basic, but its unshared electrons are not tied up in bonding and
are ready to react. Protonation occurs at the oxygen first.

+
+ H

O O

H
 The pi-bond is now poised to attack the three membered ring from the back at the most highly
substituted carbon, to open it. At the same time, a tertiary carbocation forms at one of the carbons
originally sharing the pi-bond. A new bond forms between carbons 2 and 7, which results in
formation of a new 6-membered ring.

3 2
3
1
4 2 1
4 3o cation

5
5
6
7 6 7
O O

H H

The tertiary cation undergoes an elimination reaction, losing the adjacent proton to make the new
pi-bond present in the product.

H
3
4 43
H 2O 21
2
5 1
5 + H3 O +
7
6
6
7 HO

28)2
8 Br OH
) NaOCH3 / CH3OH OsO4 / H2O2
-
(E2) or KMnO4 / OH
OH
(syn hydroxylation)

29)29)
Br OH
NaOCH3 / CH3OH 1) CH3CO3H
+ enantiomer
(E2) + -
2) H3O or OH
(anti hydroxylation)
OH

30)
OH
OH
H2SO4 1) Hg(OAc)2 / H2O

(acid-cat. E1) 2) NaBH4

(oxymerc.-demerc.)

Markovnikov alcohol
3-methyl-2-butanol
(2-methyl-2-butanol)

31) B 32) CH3CH2CH2CH2CH=CH2 33) A 34) microscopic reversibility

35) C 36) B 37) E 38) C